Process for treating hydrocarbonaceous material using catalysts made from a new aluminum trihydroxide phase

ABSTRACT

A process for treating a hydrocarbonaceous material comprising contacting such material with catalysts made from a newly discovered phase of aluminum trihydroxide.

[0001] This application is a division of application Ser. No.09/717,753, filed Nov. 21, 2000, pending.

FIELD OF THE INVENTION

[0002] This invention relates to a newly discovered phase of aluminumtrihydroxide. This invention further relates to catalysts made from thisnew phase of aluminum trihydroxide, which catalysts may be specificallyformulated to provide improved performance characteristics for a greatnumber of hydrocarbon processing operations. This invention also relatesto methods of producing this new phase of aluminum trihydroxide andcatalysts made therefrom, and to a method of improving the activity ofcatalysts having a silica-alumina support.

BACKGROUND OF THE INVENTION

[0003] The art relating to alumina-containing supports, impregnatingsuch supports with various catalytically active metals, metal compoundsand/or promoters, and various uses of such impregnated supports ascatalysts, is extensive and relatively well developed. As a few of themany exemplary disclosures relating to these fields may be mentioned thefollowing United States patents, all of which are incorporated herein byreference for all purposes as if fully set forth U.S. Pat. Nos.2,838,444; 2,935,463; 2,973,329; 3,032,514; 3,058,907; 3,124,418;3,152,865; 3,232,887; 3,287,280; 3,297,588; 3,328,122; 3,493,493;3,623,837; 3,749,664; 3,778,365; 3,897,365; 3,909,453; 3,983,197;4,090,874; 4,090,982; 4,154,812; 4,179,408; 4,255,282; 4,328,130;4,357,263; 4,402,865; 4,444,905; 4,447,556; 4,460,707; 4,530,911;4,588,706; 4,591,429; 4,595,672; 4,652,545; 4,673,664; 4,677,085;4,732,886; 4,797,196; 4,861,746; 5,002,919; 5,186,818; 5,232,888;5,246,569; 5,248,412 and 6,015,485.

[0004] While the prior art shows a continuous modification andrefinement of such catalysts to improve their catalytic activity, andwhile in some cases highly desirable activities have actually beenachieved, there is a continuing need in the industry for even higheractivity catalysts, which are provided by the present invention.

[0005] Much of the effort to develop higher activity catalysts has beendirected toward developing supports that enhance the catalytic activityof metals that have been deposited thereon. In an overwhelming majorityof applications the material chosen for a support is alumina, most oftenγ-alumina, but silica-alumina composites, zeolites and various otherinorganic oxides and composites thereof have been and are employed assupport materials. In the case of alumina, various researchers havedeveloped methods for preparing supports having various surface areas,pore volumes and pore size distributions that, when appropriate metalsare applied, are particularly suited for catalyzing a desired reactionon a particular feedstock, whether that reaction be directed towardhydrodesulphurization, hydrodemetallation, hydrocracking, reforming,isomerization and the like.

[0006] In most cases, the γ-alumina supports are produced by activation(usually calcination) of pseudo-boehmite (AlOOH) starting material. Onrare occasions, the support has been generated from one of theheretofore known aluminum trihydroxides (Al(OH)₃), Gibbsite, Bayerite orNordstrandite. When Bayerite or Nordstrandite is used as startingmaterial, the resulting dehydrated alumina has a structure differentfrom the more typical γ-alumina, often referred to as η-alumina; forGibbsite, the product alumina can be χ-alumina. Each of thesetransitional aluminas possesses different textures (porosities andsurface areas) from the more common γ-alumina. However, they generallysuffer from lower thermal stability than γ-alumina; for a specificdehydration and calcination procedure, the loss of surface area forthese aluminas is much greater than would be experienced by γ-alumina.U.S. Pat. No. 6,015,485 teaches a way to enhance the texture ofγ-alumina supported catalysts by the in-situ synthesis of a crystallinealumina on the γ-alumina base support. From that teaching, higheractivity catalysts have been produced.

[0007] As an example of the need for higher activity catalysts may bementioned the need for a higher activity first stage hydrocrackingcatalyst. In a typical hydrocracking process, higher molecular weighthydrocarbons are converted to lower molecular weight fractions in thepresence of a hydrocracking catalyst which is normally a noble metalimpregnated silica-alumina/zeolite. State-of-the-art hydrocrackingcatalysts possess a very high activity and are capable of cracking highvolume throughputs. Such catalysts, however, are highly sensitive tocontaminants such as sulfur, metals and nitrogen compounds, whichconsequently must be removed from the hydrocarbon stream prior to thecracking. This is accomplished in first stage hydrocracking processessuch as hydrodenitrogenation, hydrodesulfurization andhydrodemetallation. Hydrotreating catalysts utilized in these processesare typically a combination Group VIB and Group VIII metal impregnatedalumina substrate. State-of-the-art hydrotreating catalysts, however,are not sufficiently active to allow processing of the same high volumethroughputs as can be processed by the hydrocracking catalysts. As such,the first stage hydrocracking processes form a bottleneck in the overallhydrocracking process, which must be compensated, for example, in thesize of the hydrotreating unit relative to the hydrocracking unit.

SUMMARY OF THE INVENTION

[0008] In accordance with the present invention, there is provided, inone aspect, a newly discovered phase of aluminum trihydroxide that isproduced by hot-aging formed and calcined silica-alumina support madefrom amorphous alumina-rich silica-alumina powder in an acidic, aqueousenvironment. This newly discovered aluminum trihydroxide phase, hereinnamed “Kamenetsite”, can be distinguished from the three previouslyknown phases, Gibbsite, Bayerite and Nordstrandite, by X-ray Diffractionanalysis. When subjected to drying and calcination, Kamenetsite forms amaterial that is texturally and structurally different from othersupports. The catalysts made from this material exhibit exceptionallyhigh catalytic activity in many hydrotreating and non-hydrotreatingreactions. Indeed, by appropriate adjustment of the aging conditionsused in the production of Kamenetsite, the final texture of the catalystcan be tailored to a specific catalytic application. There is evidencethat catalysts containing the same active metals and active metalsloading perform differently with certain petroleum feedstocks dependingupon the size and concentration of the crystalline alumina particlesproduced from different Kamenetsite-containing support precursors.

[0009] Also provided in this invention is a method of making Kamenetsitefrom amorphous alumina-rich silica-alumina powder. This method involvesprocess steps that are similar to those taught in an earlier patent(U.S. Pat. No. 6,015,485). In the present invention, however, thestarting material is different from that used in '485 and the product ofthe process may be distinguished by the size and concentration of thecrystalline alumina particles produced and in the performance ofcatalysts made from the support produced.

[0010] In another aspect, the present invention provides high activitycatalysts comprising supports based upon Kamenetsite and impregnatedwith one or more metals from Group VIB and Group VIII of the PeriodicTable.

[0011] In addition to the above catalyst, the present invention alsoprovides a process for improving the activity of a catalyst compositioncomprising a particulate porous support comprising silica-alumina andamorphous alumina, and impregnated with one or more catalytically activemetals, by the steps of:

[0012] (1) wetting the catalyst composition by contact with a chelatingagent in a carrier liquid;

[0013] (2) aging the so-wetted substrate while wet;

[0014] (3) drying the so-aged substrate at a temperature and underconditions to substantially volatilize the carrier liquid; and

[0015] (4) calcining the so-dried substrate.

[0016] This process can readily be applied to existing catalystscomprising a particulate porous support containing silica-alumina andamorphous alumina, or can be utilized in a catalyst manufacture processconcurrently with and/or subsequent to the impregnation of the supportcontaining silica-alumina and amorphous alumina, with one or morecatalytically active metals and/or compounds thereof. In addition, theprocess can be utilized to improve the activity of spent catalystsduring regeneration, which spent catalysts comprise a particulate poroussupport containing silica-alumina and amorphous alumina, wherein thespent catalyst is wetted as in step (1) above subsequent to the removalof carbonaceous deposits therefrom, followed by steps (2), (3) and (4).

[0017] By performing these steps in the indicated order, it is believed(without wishing to be bound by any particular theory) that aninteraction takes place between at least the silica-alumina, amorphousalumina, chelating agent and aqueous acid which, when subjected to thetemperature and time conditions of the aging step, results in theappearance of Kamenetsite. Upon drying and calcining the product fromthis reaction a crystalline phase of alumina that may be distinguishedfrom that produced in U.S. Pat. No, 6,015,485 by the size andconcentration of the crystalline alumina particles produced. Crystallitesize at the catalyst surface can be measured via well-known techniquesinvolving transmission electron microscopy.

[0018] Concurrent with the appearance of this crystalline phase, anincrease in the surface area of the catalyst is also achieved. Inaddition, in preferred embodiments, a structure is generated with aporosity peaking in a first region of pore size 40 Å or less, and morepreferably in the range of 20 Å to 40 Å, as measured by nitrogenporosimetry using the desorption isotherm.

[0019] The resulting high activity catalysts find use in a wide varietyof fields as detailed in the many previously incorporated references. Aparticularly preferred use is as a first stage hydrocracking catalyst inhydrodenitrogenation, hydrodesulfurization and hydrodemetallation.

[0020] These and other features and advantages of the present inventionwill be more readily understood by those of ordinary skill in the artfrom a reading of the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

[0021]FIG. 1 shows the FTIR spectra of the aluminum trihydroxide of thepresent invention, aged at 90° C. for 1 day and for 25 days, and of1-day-aged material spectrum subtracted from the 25-day-aged materialspectrum.

[0022]FIG. 2 shows the FTIR spectra for boehmite, Bayerite, Gibbsite andNordstrandite.

[0023]FIG. 3 shows a 22 hour scan X-Ray Diffraction pattern for thesample aged for 25 days at 90° C. The marked lines are for Kamenetsite.Several unmarked lines present below 5 Å d-spacing, are due to organicspecies present in the oven-dried sample. There are also broaddiffraction lines attributable to the γ-alumina support and the activemetal oxides.

DETAILED DESCRIPTION OF THE INVENTION

[0024] A. New Aluminum Trihydroxide Phase (Kamenetsite)

[0025] Starting Material

[0026] The preferred starting material for the production of Kamenetsiteis silica-alumina powder containing a substantial percentage ofamorphous alumina. A measurable concentration of Kamenetsite may beproduced from powder comprising as little as 4 wt. % silica and thebalance alumina, at least about 20 wt. % of which is amorphous aluminaand from a powder comprising as much as 8 wt. % silica and the balancealumina, at least about 30 wt. % of which is amorphous alumina.Preferably, the starting material contains between about 5 wt. % andabout 7 wt. % silica and the balance alumina, with between about 20 wt.% and about 50 wt. % of the alumina being amorphous.

[0027] Method of Making

[0028] The new aluminum hydroxide phase of this invention may beprepared by:

[0029] (1) wetting the starting material by contact with a chelatingagent in a carrier liquid and an acidic solution of a metal compound;

[0030] (2) aging the so-wetted starting material while wet at conditions(i.e., a combination of temperature and duration of aging) that willproduce the desired amount of Kamenetsite, preferably at temperatureshigher than 50° C. for from 1 to 10 days;

[0031] (3) drying the so-aged starting material at a temperature andunder conditions to substantially volatilize the carrier liquid; and

[0032] (4) calcining the so-dried material.

[0033] Chelating agents suitable for use in this process include thoseknown to form more stable complexes with transition metals and aluminumand, consequently, possess high stability constants with respectthereto. Particularly preferred for use in the present invention isethylenediaminetetraacetic acid (EDTA) and derivatives thereofincluding, for example, N-hydroxy ethylenediaminetetraacetic acid anddiammonium ethylenediaminetetraacetic acid. Also suitable aretris(2-aminoethyl)amine and triethylenetetraamine. Other candidatesinclude diethylenetriaminepentaacetic acid,cyclohexanediaminetetraacetic acid,ethyleneglycol-bis-(beta-aminoethylether)-N,N′-tetraacetic acid,tetraethylenepentaamine and the like. The suitability of other chelatingagents can be readily determined by those of ordinary skill in the artby treating a starting material sample in accordance with the presentinvention and then, prior to drying and calcining the sample,determining with the aid of transmission electron microscopy or X-rayDiffraction whether or not Kamenetsite of appropriate crystallite sizehas formed.

[0034] The amount of chelating agent utilized is not critical toproducing Kamenetsite, but does have an influence on the amountproduced. Widely varying amounts of chelating agent can be utilizeddepending on a number of factors such as solubility in the carrierliquid, type of catalyst support and metals impregnated or to beimpregnated thereon. Generally, the starting material should be wettedby a carrier liquid containing the chelating agent in amounts rangingfrom 0.01-1.0 grams of chelating agent per gram of starting material.

[0035] The material may be wetted by any normal method such as dippingor spraying. To ensure adequate infiltration of the chelating agent,dipping is preferred followed by a soaking period. The preferred carrierliquid is water or a water/ammonia solution.

[0036] The length of time necessary for aging of the wet startingmaterial is a function of the temperature during aging. At roomtemperature, it is preferred to age the wetted substrate for at least 30days, more preferably at least 60 days. As temperature increases, therequired aging time decreases. At 80° C., it is preferred to age thewetted material for at least two days, more preferably at least threedays. Preferably, aging is accomplished at a temperature in the range of20° C. to 90° C.

[0037] Subsequently, the aged material is dried to substantially removethe carrier liquid. It is preferred that the drying take place slowly atfirst and then rapidly at elevated temperatures in the range of 100° C.to 250° C. Preferably, a forced air heater is utilized to speed dryingto a preferred time of less than one hour.

[0038] The so-dried material is then calcined under conditionswell-known to those of ordinary skill in the art. Preferably, however,the calcination takes place in two stages—a first lower temperaturestage in which the temperature is sufficiently high to drive off ordecompose any remaining chelating agent, but which is not so high thatthe chelating agents combust to form carbonaceous deposits. This firststage temperature will vary depending on the particularly chelatingagent, but typically a temperature within the range of 250° C. to 350°C. will be sufficient. Once any remaining chelating agent issubstantially removed, the catalyst may then be calcined under thenormal higher temperature conditions commonly utilized.

[0039] B. Catalysts

[0040] Method of Making Kamenetsite-containing Catalysts

[0041] The procedure for making Kamenetsite described above may beadapted for producing a finished catalyst. The starting material mayfirst be formed into the desired support shape by methods known to thoseskilled in the art. The formed, calcined support can then be wetted withthe chelating agent/carrier liquid either prior to, concurrently withand/or subsequent to the impregnation of the support with theappropriate catalytically active metals, followed by steps (2) through(4) as described above. It is only important to ensure that the agingstep takes place while the impregnated support is wet from the carrierliquid for the chelating agent and the acidic solution of impregnationmetals.

[0042] Catalytically Active Metals

[0043] The present invention is applicable to catalysts impregnated withone or more of a wide variety of catalytically active metals well-knownto those of ordinary skill in the art as exemplified, for example, bythe numerous incorporated references. In the context of the presentinvention, “catalytically active metals” includes both the metalsthemselves as well as metal compounds. In addition to the catalyticallyactive metals, the catalysts may also be impregnated with one or morewell-known promoters such as phosphorous, tin, silica and titanium(including compounds thereof).

[0044] Typically, the catalytically active metals are transition metalsselected from the group consisting of Group VIB metals, Group VIIImetals and combinations thereof. The specific choice of metal(s),promoter(s) and loadings, of course, depends upon the desired end use ofthe catalyst, and these variables can readily be adjusted by those ofordinary skill in the art based upon the end use. As specific examplesthereof may be mentioned the following (wt % is based on the totalcatalyst weight): Hydrotreating Operations Hydrodenitrogenation Niand/or Co, and preferably Ni, in an amount up to 7 wt % calculated asNiO and/or CoO Mo and/or W, preferably Mo, in an amount up to 35 wt. %calculated as MoO₃ and/or WO₃ optionally P, and preferably including P,in an amount up to 10 wt % calculated as P₂O₅ Hydrodesulfurization Niand/or Co, and preferably Co, in an amount up to 9 wt % calculated asNiO and/or CoO Mo and/or W, preferably Mo, in an amount up to 35 wt %calculated as MoO₃ and/or WO₃ optionally P, and preferably including P,in an amount up to 10 wt % calculated as P₂O₅ Hydrodemetallationoptionally Ni and/or Co, and preferably including Ni and/or Co, in anamount up to 5 wt % calculated as NiO and/or CoO Mo and/or W, preferablyMo, in an amount up to 20 wt % calculated as MoO₃ and/or WO₃ optionallyP, and preferably including P, in an amount up to 10 wt % calculated asP₂O₅ Hydroconversion Ni and/or Co, and preferably Ni, in an amount up to5 wt % calculated as NiO and/or CoO Mo and/or W, preferably Mo, in anamount up to 20 wt % calculated as MoO₃ and/or WO₃ optionally P, andpreferably including P, in an amount up to 6 wt % calculated as P₂O₅Hydrocracking Ni and/or Co, and preferably Ni, in an amount up to 5 wt %calculated as NiO and/or CoO Mo and/or W, preferably Mo, in an amount upto 20 wt % calculated as MoO₃ and/or WO₃ optionally P, and preferablyincluding P, in an amount up to 10 wt % calculated as P₂O₅Hydrogenation/ a noble metal, and preferably Pt or Pt in combinationwith Dehydrogenation Rh, in an amount up to 2 wt % calculated on anelemental basis Reforming a noble metal, and preferably Pt or Pt incombination with another noble metal such Re and/or Ir, and/or Sn, in anamount up to 2 wt % calculated on an elemental basis Non-HydrotreatingOperations Isomerization a noble metal, and preferably Pt or Pt incombination with another noble metal, in an amount up to 2 wt %calculated on an elemental basis Claus Process Ni and/or Co, andpreferably Ni, in an amount up to 5 wt % calculated as NiO and/or CoO Moand/or W, preferably Mo, in an amount up to 20 wt % calculated as MoO₃and/or WO₃ optionally P, and preferably including P, in an amount up to6 wt % calculated as P₂O₅

[0045] Such catalysts are prepared by impregnating the supports with theappropriate components, followed by various drying, sulfiding and/orcalcining steps as required for the appropriate end use. Such catalystpreparation is generally well-known to those of ordinary skill in therelevant art, as exemplified by the numerous previously incorporatedreferences, and further details may be had by reference thereto ornumerous other general reference works available on the subject.

[0046] Catalyst Regeneration

[0047] As indicated above, the process in accordance with the presentinvention is not only applicable to pre-formed catalysts, but also canbe applied to regenerated catalysts in a like manner. Specifically,subsequent to the removal of carbonaceous material from a spent catalystvia well-known procedures, such catalysts are then be treated by steps(1) through (4) in an identical manner as described above.

[0048] Catalysts Tailored to a Specific Operation

[0049] By careful selection of temperature and time during the agingstep, the concentration and crystallite size of the Kamenetsite alongwith its ultimate pore structure can be modified. The modified catalystthen displays a different response to, for example, thehydrodesulfurization of a pair of gas oils. One possibility fortailoring a catalyst of the present invention is discussed in Example 9below. Example 9 is meant to be illustrative of the possibilities thataccrue from the present invention and is not intended to be limiting inany way. Those skilled in the art are capable of identifying other suchopportunities.

[0050] C. Characterization of Kamenetsite

[0051] X-ray diffraction analysis using copper Kα radiation of crystalsof the newly discovered aluminum trihydroxide phase confirm that thematerial is different from the three previously known phases of aluminumtrihydroxide. As shown in Table 1 below, Kamenetsite exhibits a verystrong peak at 2θ=18.33°, the same angle as the major peak for Gibbsiteand reasonably close to the major peaks of Nordstrandite and Bayerite.Across the remainder of the diffraction pattern, however, Kamenetsiteshows significant peaks at diffraction angles where the other phases donot and does not show peaks at angles where they do. The positions ofthe Kamenetsite diffraction lines are quoted here to a relativeprecision of 1% (95% Confidence Index) and relative intensities to arelative precision of 10% (95% CI). TABLE 1 Diffraction Line RelativeIntensity 2θ, ° Kamenetsite (1) Gibbsite (2) Nordstrandite (2) Bayerite(2) 18.33 100 100 — — 18.50 — — 100 — 18.80 — — — 100 20.25-20.55 — 3630 70 27.63 3 — — — 35.12 5 — — — 36.47 25 — — — 37.55 — — 30 — 39.76 —— 30 — 39.87 38 — — — 40.50 — — — 100 52.09 33 — — — 63.12 6 — — —

[0052] Kamenetsite crystallite size and the integrated intensity of theX-ray diffraction line at 2θ=18.33° both increase with increased agingtemperature and duration of aging as shown in Table 2. TABLE 2Integrated Intensity Aging of line at Temperature, Duration ofCrystallite 2θ = 18.33°, ° C. Aging, days Size, A counts 90 1 35 1972 248 2354 3 55 3086 5 61 3510 7 64 4039 10 72 4438 80 1 23 2165 75 3 241246

[0053] Thermogravimetric Analysis (TGA) and X-ray diffraction ofKamenetsite-containing materials heated to high temperatures show thedisappearance of the major peak at 2θ=18.33° at about 250° C. Since 250°C. is the known transformation temperature of aluminum trihydroxides totransition aluminas, these data confirm that the new material is adistinct new phase of aluminum trihydroxide.

[0054] In addition, Fourier Transform Infra-Red (FTIR) spectroscopyanalysis has been carried out on the 90° C., 1-day-aged and 25-day-agedlow-temperature dried products. These spectra are shown in FIG. 1. Theenhanced presence of Kamenetsite in the 25-day-aged material is clearlyseen when the 1-day-aged material spectrum is subtracted from the25-day-aged material spectrum, shown as the “difference” spectrum at thebottom of FIG. 1. FTIR bands at 3512, 989, and 521 wave numbers in the“difference” spectrum confirm the presence of Al(OH)₃. For comparison,the FTIR spectra of boehmite, Bayerite, Gibbsite and Nordstrandite areshown in FIG. 2.

[0055] Comparison with Material Produced without Silica in the StartingMaterial

[0056] The appearance of Kamenetsite in material produced by the processof the present invention is not readily apparent when the startingmaterial contains less than about 4 wt. % silica. A correlation has beendeveloped, however, that permits the indirect determination of theamount of Kamenetsite contained in the product of the process of thepresent invention. This correlation relates the amount of Kamenetsite ina product to its texture as determined by its porosity measured by theadsorption of nitrogen. Based upon an extrapolation of this correlation,it is possible to conclude that a small amount of Kamenetsite isprobably present in material produced using silica-free alumina as astarting material. The data showing these extrapolated values forKamenetsite in materials produced from such silica-free alumina areshown in Examples D and E.

EXAMPLES

[0057] The present invention as described above will be furtherexemplified by the following specific examples which are provided by wayof illustration and not limitation thereof.

Test Conditions

[0058] Test conditions used in comparing the performance of catalysts ofthe present invention against those of U.S. Pat. No. 6,015,485 and astandard refinery catalyst are: Test Type A Feedstock: Straight-run gasoil for North American refiner. Sulfur, wt. %: 1.25 Total Nitrogen, ppm65 Density, g/cc 0.848 Aromatics, wt. % 8.63 Diaromatics, wt. % 2.63Distillation, ° C.: Initial 114.5 50% 286.7 95% 368.9 Test Conditions:Temperature, ° C. 343 Pressure, psig 590 Gas Rate, SCF/B 1000 LiquidHourly Space Velocity (LHSV), hr⁻¹ 2 Test Type B Feedstock: Straight-runlight Arabian gas oil for European refiner. Sulfur, wt. %: 1.77 TotalNitrogen, ppm 183 Density, g/cc 0.863 Aromatics, wt. % 12.94Diaromatics, wt. % 4.46 Distillation, ° C.: Initial 175 50% 290.6 95%366.7 Test Conditions: Temperature, ° C. 360 Pressure, psig 588 GasRate, SCF/B 1000 Liquid Hourly Space Velocity (LHSV), hr⁻¹ 1, 2 and 3Test Types C₁, C₂, C₃ Feedstock: Gas Oil blend Sulfur, wt. %: 1.637Total Nitrogen, ppm 401 Density, g/cc 0.887 Test Conditions:Temperature, ° C. C₁= 343; C₂ = 357; C₃ = 371 Pressure, psig 675 GasRate, SCF/B 1200 Liquid Hourly Space Velocity (LHSV), hr⁻¹ 2.7 Test TypeD Feedstock: Straight-Run/Light Cycle Gas Oil blend Sulfur, wt. %: 0.8Total Nitrogen, ppm 196 Density, g/cc 0.889 Test Conditions:Temperature, ° C. 349 Pressure, psig 580 Gas Rate, SCF/B 1000 LiquidHourly Space Velocity (LHSV), hr⁻¹ 2.0 Test Types E₁, E₂ Feedstock:Straight-Run/Light Cycle Gas Oil blend Sulfur, wt. %: 0.508 TotalNitrogen, ppm 760 Density, g/cc 0.859 Test Conditions: Temperature, ° C.E₁= 343; E₂ = 385 Pressure, psig 700 Gas Rate, SCF/B 1000 Liquid HourlySpace Velocity (LHSV), hr⁻¹ 2.4 Test Type F Feedstock: Straight-RunLight Arabian Gas Oil Sulfur, wt. %: 1.005 Total Nitrogen, ppm 251Density, g/cc 0.864 Test Conditions: Temperature, ° C. 363 Pressure,psig 580 Gas Rate, SCF/B 1000 Liquid Hourly Space Velocity (LHSV), hr⁻¹3.0

Example 1

[0059] This example describes the preparation of samples of catalysts ofthe present invention.

[0060] A powder comprising alumina particles coated with 6 wt. % silicawas mulled, extruded into a trilobe shape, dried and calcined byconventional means. Details of the 6 wt. % silica-alumina powder hasbeen described in the open literature (McMillan M., Brinen, J. S.,Carruthers, J. D. and Haller, G. L., “A ²⁹Si NMR Investigation of theStructure of Amorphous Silica-Alumina Supports”, Colloids and Surfaces,38 (1989) 133-148). The powder used here met the criterion for porositystability as described in the above publication.

[0061] 95.6 grams of the silica-alumina support was impregnated toincipient wetness with 100 ml of solution “A”. The solution, designatedherein as solution “A”, consisted of a mixture of two solutions:solution “C” prepared by adding 11.3 grams of ammonium hydroxidesolution (28 wt. %) to 65.3 grams of Dow Versene, Tetraammoniumethylenediaminetetraacetic acid solution (38.0% as EDTA) and solution“D”. Solution “D” was prepared by adding 4.37 grams of ammoniumhydroxide solution (28 wt. %) to 41.0 grams of solution “E”. Thesolution, designated herein as solution “E”, was prepared by adding 137grams of cobalt carbonate solid to 500 grams of a dilute solution ofphosphoric acid (23.0 grams of H₃PO₄—86.0 wt. %—and 475 grams ofdeionized water), heating the mixture to 55° C. and then adding 300grams of Climax MoO₃. The mixture was then heated to 98° C. withstirring for 1.5 hrs at which point 100 grams of nitric acid solution(70 wt. %) were added to fully dissolve the mix. This solution,designated herein as Solution “E”, of phosphoric acid containing cobaltand molybdenum compounds wherein the Co/Mo weight ratio was 0.258 andhaving a pH of approximately 0.6 was then cooled to room temperature and41.0 grams of the solution were used to prepare solution designatedherein as solution “D”.

[0062] The wet pills were allowed to stand for 2 hours and then dried inan oven in a shallow layer at 230° C. for 1 hour. 122.6 grams of driedproduct were then dipped into a container of solution “E” and 360 gramsof this solution were then circulated to wash the pills. The wet pillswere then separated from the excess solution by centrifugation andplaced in a sealed bottle in an oven set at 75° C. and held at thattemperature for 3 days. The material was then fast-dried at 230° C. for20 minutes to volatilize the carrier liquid to an LOI of 30-32 wt. %,followed by calcination at 500° C. for one hour in air to produce acatalyst of the present invention, designated herein as Catalyst C-2.Catalyst C-2 contained 5.97 wt. % Co, 19.7 wt. % Mo and 0.77 wt. % P andhad a surface area of 305 m²/g and estimated Kamenetsite intensity of3344 counts.

[0063] A second 100 gram portion of the support was wetted to incipientwetness with a solution comprising 62.5 grams of Dow Versene diammoniumethylenediaminetetraacetic acid solution (40.0 wt. % as EDTA) and 77.59grams of solution designated herein as solution “F”. Solution “F” wasprepared by adding 329 grams of MoO₃, 100.0 grams of Co(OH)₂ and 282.6grams of citric acid monohydrate to 695 grams of deionized water andheated from room temperature to 80° C. The solution was then boiled forapproximately one hour until all components became fully dissolved andthen cooled to room temperature. Solution “F” contained cobalt andmolybdenum compounds wherein the Co/Mo weight ratio was 0.292 with a pHof approximately 0.6. The wet pills were allowed to soak for one hourfollowed by drying in a shallow layer in a dryer at 230° C. for onehour.

[0064] The dried pills were then immersed in 300 grams of solution “F”and the solution circulated over the pills for one hour. The wet pillswere separated from the solution by centrifugation and placed in asealed bottle in an oven set at 75° C. for 3 days. The material was thenfast-dried at 230° C. for 1 hour to volatilize the carrier liquid to anLOI of 30-32 wt. %, and then calcined at 500° C. for I hour to produce acatalyst of the present invention, designated herein as Catalyst D-2.Catalyst D-2 contained 4.11 wt. % Co and 16.3 wt. % Mo and had a surfacearea of 347 m²/g and estimated Kamenetsite intensity of 4320 counts.

[0065] A third 100 gram portion of the support was wetted to incipientwetness with a solution containing 64.7 grams of Dow Versene diammoniumethylenediaminetetraacetic acid (40.0 wt. % as EDTA) with 82.3 grams ofa solution, designated herein as Solution “G”. Solution “G” was preparedby adding 300 grams of MoO₃ and 137.5 grams of CoCO₃ to 575 grams ofdeionized water followed by heating to 70-80° C. with stirring, and thenadding slowly 225.0 grams of citric acid monohydrate. The solution wasthen boiled to complete dissolution for 30 minutes and then allowed tocool. Solution “G”, containing cobalt and molybdenum compounds whereinthe Co/Mo weight ratio was 0.321 had a pH of approximately 2.0. The wetpills were allowed to stand for 1 hour and then dried in a shallow layerin an oven set at 230° C. for an hour.

[0066] The dried pills were then immersed in 300 grams of solution “G”and the solution circulated over the, pills for one hour. The wet pillswere separated from the solution by centrifugation and placed in asealed bottle in an oven set at 75° C. for 3 days. The material was thenfast-dried at 230° C. for one hour to volatilize the carrier liquid toan LOI of 30-32 wt. %, and then calcined at 500° C. for an additionalhour to produce a catalyst of the present invention, designated hereinas Catalyst E-2. Catalyst E-2 contained 4.53 wt. % Co and 14.6 wt. % Moand had a surface area of 310 m²/g and estimated Kamenetsite intensityof 1082 counts.

Example 2 Comparative

[0067] This example describes the preparation of samples of catalysts ofU.S. Pat. No. 6,025,485.

[0068] A support was made using the same procedure as in Example 1,except that the starting material contained no silica.

[0069] A portion of this support was treated in the same manner asCatalyst C-2 to yield Catalyst C-1. Catalyst C-1 contained 4.67 wt. %Co, 18.1 wt. % Mo and 0.61 wt. % P and had a surface area of 280 m²/gand estimated Kamenetsite intensity of 195 counts.

[0070] A second portion of this support was treated in the same manneras Catalyst D-2 to yield Catalyst D-1. Catalyst D-1 contained 4.08 wt. %Co and 14.7 wt. % Mo and had a surface area of 230 m²/g and estimatedKamenetsite intensity of less than 100 counts.

Example 3 Comparative

[0071] This example describes the preparation of two catalysts preparedby the method of the present invention but with insufficient and withmarginally sufficient silica in the starting material to produce acatalyst of the present invention.

[0072] A support was made using the same procedure as in Example 1,except that the starting material contained 2 wt. % silica. This supportwas treated in the same manner as Catalyst E-2 to yield Catalyst E-1.Catalyst E-1 contained 5.91 wt. % Co and 19.7 wt. % Mo and had a surfacearea of 215 m²/g and estimated Kamenetsite intensity of 300 counts.

[0073] A second support was made using the same procedure as in Example1, except that the starting material contained 3.7 wt. % silica, lowerthan the preferred (6 wt. %) yet higher than the 2 wt. % used forCatalyst E-1. This support was treated in the same manner as CatalystD-2 to yield Catalyst D-3. Catalyst D-3 contained 4.08 wt. % Co and 15.7wt. % Mo and had a surface area of 245 m2/g and estimated Kamenetsiteintensity of 1880 counts.

Example 4

[0074] This example compares the performance of Catalyst C-2 to CatalystC-1 and a refinery standard catalyst (“Standard”), manufactured byconventional means.

[0075] Each catalyst was subjected to Test Type A. The results arepresented in Table 3: TABLE 3 Catalyst S_(product), wppm RVA (1)Standard 330 100 C-1 175 143 C-2 91 202

[0076] This test shows that Catalyst C-2, that of the present invention,is more effective at removing sulfur than either of the other twocatalysts.

Example 5

[0077] This example compares the performance of Catalyst D-2 to CatalystD-1 and a refinery standard catalyst (“Standard”), manufactured byconventional means.

[0078] Each catalyst was subjected to Test Type B. The results arepresented in Table 4: TABLE 4 Catalyst S_(product), wppm RVA (1)Standard 350 100 D-1 350 117 D-2 350 143

[0079] This test shows that a lesser amount of Catalyst D-2 of thepresent invention is required to achieve a desired sulfur level in theproduct than either of the other two catalysts. Example 6

[0080] This example compares the performance of Catalyst E-2 to CatalystE-1 and a refinery standard catalyst (“Standard”), manufactured byconventional means.

[0081] Each catalyst was subjected to Test Type B. The results arepresented in Table 5: TABLE 5 Catalyst S_(product), wppm RVA (1)Standard 350 100 E-1 350 102 E-2 350 124

[0082] This test shows that a lesser amount of Catalyst E-2 of thepresent invention is required to achieve a desired sulfur level in theproduct than either of the other two catalysts. The test also shows thatthe use of a starting material containing insufficient silica in thecatalyst preparation procedure of the present invention produces acatalyst, i.e., Catalyst E-1, that is no more effective than a standardrefinery catalyst.

Example 7

[0083] This example describes the preparation of samples of catalysts ofthe present invention in which both Ni and Co are included in thefinished catalyst and the preparations are subjected to significantlydifferent aging conditions.

[0084] 100 grams of the silica-alumina support described in Example 1was impregnated to incipient wetness with 152.4 grams of solution “K”.The solution, designated herein as solution “K” consisted of a mixtureof two solutions: 68.0 grams of solution “L” prepared by adding 6.66grams of solid nickel acetate (23.58 wt. % Ni metal) to 99.54 grams ofDow Versene diammonium ethylenediaminetetraacetic acid solution (40 wt.% as EDTA) and 84.4 grams of solution “F” described in Example 1, above.

[0085] The wet pills were allowed to stand for 2 hours as before andthen dried in an oven in a shallow layer at 230° C. for 1 hour. 143.8grams of dried product were then dipped into a container of solution “F”and 317 grams of this solution were then circulated to wash the pills.The wet pills were then separated from the excess solution bycentrifugation and placed in a sealed bottle in an oven set at 75° C.and held at that temperature for 3 days. The material was thenfast-dried at 230° C. for 20 minutes to volatilize the carrier liquid toan LOI of 30-32 wt. %, followed by calcination at 500 ° C. for one hourin air to produce a catalyst of the present invention, designated hereinas Catalyst A. Catalyst A contained 4.3 wt. % Co, 17.0 wt. % Mo and 0.68wt. % Ni and had a surface area of 347 m²/g and estimated Kamenetsiteintensity of 2670 counts.

[0086] A second preparation followed the identical scheme for Catalyst Abut was aged at 90° C. for 7 days instead of the 75 ° C. for 3 days.This catalyst was designated herein as Catalyst B. Catalyst B contained4.24 wt. % Co, 16.8 wt. % Mo and 0.68 wt. % Ni and had a surface area of340 m²/g and estimated Kamenetsite intensity of 6138 counts.

Example 8

[0087] This example demonstrates that the activity of a catalyst of thepresent invention improves relative to that of a refinery standardcatalyst as operating conditions are intensified.

[0088] Catalyst A and a refinery standard catalyst (“Standard”),manufactured by conventional means, were each subjected to Test TypesC₁, C₂ and C₃, which were identical except that operating temperatureincreased from C₁ through C₃. The test results are presented in Table 6.TABLE 6 Test Type C₁ C₂ C₃ RVA-HDS RVA-HDS RVA-HDS Catalyst (1)S_(product) (1) S_(product) (1) S_(product) Standard 100 797 100 420 100209 A 132 584 144 261 159 112

[0089] Note the increase in the relative volume activity as operatingtemperature is increased from 343° C. to 357° C. to 371° C. These datashow that the performance of a catalyst of the present inventionrelative to that of a refinery standard catalyst increases as operatingconditions are intensified.

Example 9

[0090] This example illustrates the ability to tailor catalysts of thepresent invention to the operating conditions that are expected.

[0091] Catalyst A, Catalyst B and a refinery standard catalyst(“Standard”), manufactured by conventional means, were each subjected toTest Types D, E₁ and E₂. The feedstock for Test Type D contained amoderate concentration of nitrogen (196 wppm), whereas the feedstock forTest Types E₁ and E₂ had a high nitrogen content (760 wppm).

[0092] In this example the performance the Catalyst A of the inventionis contrasted with the performance of Catalyst B prepared with a muchhigher concentration of Kamenetsite in its precursor material. Thisincrease in Kamenetsite was achieved by increasing both the temperatureand the time during the aging step. This enhanced aging increased theconcentration and the crystallite size of the Kamenetsite. Along withthe change in Kamenetsite, the pore structure of the final catalystunderwent significant change. The modified catalyst then displayed aquite different response to an increase in temperature duringhydrodesulfurization of just one of the gas oils. This can be seen inthe following test results, presented in Table 7. TABLE 7 Test Type D E₁E₂ RVA-HDS RVA-HDS RVA-HDS Catalyst (1) S_(product) (1) S_(product) (1)S_(product) Standard 100 224 100 313 100 51 A 123 159 121 234 100 55 B130 143 128 213 131 34

[0093] In this Table the three catalysts are listed with a minimalamount of description . . . the industry-standard Reference Catalyst,Catalyst A, a catalyst of the invention prepared so that it displays amoderate concentration of Kamenetsite in the precursor material andCatalyst B, a catalyst displaying a high concentration of Kamenetsite inits precursor material. Each catalyst was then tested alongside theothers at constant temperature and pressure using two Straight-Run/LightCycle Gas Oil blends as described in Test Type D and E. G1 and G2.

[0094] Under Test Type D, both catalysts of the present invention aremore active than the Standard with the higher Kamenetsite catalystslightly better of the other (130 vs. 123 RVA). A similar result isachieved for Test Type E₁. However, notice that when the processingconditions are changed for the three catalysts in Test Type E₂, thehigher Kamenetsite-version maintains its performance advantage but thatof the lower concentration version falls back.

[0095] Without wishing to be bound by any particular theory, it isbelieved that catalysts prepared from materials high in Kamenetsitepossess more active sites per unit volume of catalyst thanconventionally prepared catalysts. In the example shown above, the twocatalysts of the invention responded differently to an increase intemperature during Test Type E₂. The Test Type E feedstock differed fromthe Test Type D gas oil primarily in the concentration ofnitrogen-containing molecules.

[0096] Under the low pressure and low hydrogen treat-rate conditions ofthese tests, removal of nitrogen-containing molecules is far fromcomplete. In addition, the unconverted nitrogen-containing moleculesbecome hydrogenated (basic) nitrogen molecules during partial(incomplete) hydrodenitrogenation of the gas oil. Such molecules areknown to reduce the activity of the desulfurization catalyst byadsorption on its more acidic sites. It is therefore reasonable topropose that the catalyst achieving more removal of nitrogen-containingmolecules (Catalyst B) and possessing more available HDS sites, willlessen the ‘dynamic poisoning effect’ of the remainingnitrogen-containing molecules and thereby maintain a higherhydrodesulfurization activity in the catalyst. These data thereforeindicate that catalysts of the invention could be tailored for optimumperformance depending upon the different concentrations ofnitrogen-containing molecules in the feedstock.

Example 10

[0097] This example compares the performance of a catalyst prepared witha “sufficient” level of silica in the silica-alumina and a catalystprepared with a “marginally sufficient” level of silica in thesilica-alumina support. Catalyst D-2 is compared to Catalyst D-3 and arefinery standard catalyst (“Standard”), manufactured by conventionalmeans, in a standard test, Test Type F. TABLE 8 Catalyst S_(product),wppm RVA (1) Standard 212 100 D-2 117 140 D-3 161 117

[0098] This test shows that the use of a starting material containingmarginally sufficient silica in the catalyst preparation procedure ofthe present invention produces a catalyst, i.e., Catalyst D-3, that ismore effective than a standard refinery catalyst but is not as active asthe catalyst with sufficient silica in the silica-alumina support,Catalyst D-2

We claim:
 1. A process for treating a hydrocarbonaceous materialcomprising contacting said hydrocarbonaceous material with a catalystcomposition comprising a support produced from an aluminum trihydroxidephase having measurable X-ray diffraction peaks between about 2θ=18.15°and about 2θ=18.50°, between about 2θ=36.1° and about 2θ=36.85°betweenabout 2θ=39.45° and about 2θ=40.30°, and between about 2θ=51.48° andabout 2θ=52.59°, and a catalytically active amount of metals.
 2. Theprocess of claim 1 further characterized in that the aluminumtrihydroxide phase has measurable X-ray diffraction peaks between about2θ=27.35° and about 2θ=27.90°, between about 2θ=34.75° and about2θ=35.48°, and between about 2θ=62.40° and about 2θ=63.80°.
 3. Theprocess of claim 1 further characterized in that the aluminumtrihydroxide phase does not have measurable X-ray diffraction peaksbetween about 2θ=20.15° and about 2θ=20.65°.
 4. The process of claim 1further characterized in that the aluminum trihydroxide phase does nothave measurable X-ray diffraction peaks between about 2θ=20.15° andabout 2θ=20.65° and between about 2θ=37.35° and about 2θ=37.75°.
 5. Theprocess of claim 1 further characterized in that the aluminumtrihydroxide phase does not have measurable X-ray diffraction peaksbetween about 2θ=18.70° and about 2θ=18.90°, between about 2θ=20.30° andabout 2θ=20.50°, and between about 2θ=40.30° and about 2θ=40.70°.
 6. Theprocess of claim 1 further characterized in that the aluminumtrihydroxide phase has measurable X-ray diffraction peaks between about2θ=27.35° and about 2θ=27.90°, between about 2θ=34.75° and about2θ=35.48°, and between about 2θ=62.40° and about 2θ=63.80°; and does nothave measurable peaks between about 2θ=18.70° and about 2θ=18.90°,between about 2θ=20.15° and about 2θ=20.65°, between about 2θ=37.35° andabout 2θ=37.75°, and between about 2θ=40.30° and about 2θ=40.70°.
 7. Theprocess of claim 1 further characterized in that the catalystcomposition further comprises a promoter.
 8. The process as set forth inany one of claims 1-7 further characterized in that the treating iscatalytic hydrodesulfurizing of a hydrocarbon-containing feed comprisingcontacting the feed under hydrodesulfurization conditions.
 9. Theprocess as set forth in any one of claims 1-7 further characterized inthat the treating is catalytic hydrodenitrogenation of ahydrocarbon-containing feed comprising contacting the feed underhydrodenitrogenation comprising contacting the feed underhydrodesulfurization conditions.
 10. The process as set forth in any oneof claims 1-7 further characterized in that the treating is catalytichydroconversion of a hydrocarbon-containing feed comprising contactingthe feed under hydroconversion conditions.
 11. The process as set forthin any one of claims 1-7 further characterized in that the treating iscatalytic hydrodemetallation of a hydrocarbon-containing feed comprisingcontacting the feed under hydrodemetallation conditions.
 12. The processas set forth in any one of claims 1-7 further characterized in that thetreating is catalytic hydrocracking of a hydrocarbon-containing feedcomprising contacting the feed under hydrocracking conditions.
 13. Theprocess as set forth in any one of claims 1-7 further characterized inthat the treating is catalytic reforming of a hydrocarbon-containingfeed comprising contacting the feed under reforming conditions.
 14. Theprocess as set forth in any one of claims 1-7 further characterized inthat the treating is catalytic hydrogenation-dehydrogenation of ahydrocarbon-containing feed comprising contacting the feed underhydrogenation-dehydrogenation conditions.
 15. The process as set forthin any one of claims 1-7 further characterized in that the treating iscatalytic isomerization of a hydrocarbon-containing feed comprisingcontacting the feed under isomerization conditions.